Primary cell



May 20, 1952 J. J. COLEMAN ET AL PRIMARY CELL Filed Nov. 20, 1948 J9 J6 J6 CARBON J5 JNVENTORS. W 560%77mv ana 08 617206? QZZ'JCKM AQd LZ-w M Patented May 20, 1952 UNHTED rare-NT- rrlce entree REMARK CELL hfilaims. 1

This invention relates toimprovements in primary cells adapted for the delivery of electrical current, and particularly-to an improved; primary cell having a non-aqueous electrolyte.

Heretofore, current producing primary oelis have employed aqueous electrolytes, The-principal reason for this is thatwater readi qni z es the electrolyte compound and such ien gation promotes electrolytic action and conductivity. It has been the belief'heretofore thatan aqueous electrolyte is necessary in order to provide the ionization required for the satisfactory production of current output.

The use of an aqueous electliqlyte however has the disadvantage that it tends to attach the negative electrode while the cell is not in operation, with the result that the cell undergoes persistent deterioration and exhaustion unless, the mentioned tendency is successfully resisted; The avoidance of excessive deterioration and exhaustion from this cause has been one of the chief problems confronting the primary battery industry. The tendency is more pronounced with the more highly electronegative metals, such as magnesium, and the use of such metals has-"been generally avoided for this reason. Thelatter are naturally more desirable becausethey'impart to the cell a higher voltage and -the-ability'- to deliver a greater amount ofelectricalflenergy but nevertheless, little use-has -been-.madeofi-themin the past because they are more susceptibleto' attack by the aqueouselectrolyte,

In accordance with the present: invention, it has been found that primary-cells having satisr factory current de y r nen cncrt esca bemadc 1 with an e r e, on aini an n- 1 1 91 5 solvent, that is, a substantially-waterafre solvent It ha n. pun that; qe. aqueous solvents dissolve. electrolyte s and otherwise function in a mannwerusueh as to provide suitable electrolytic action and iactery energy delivery performance. In .-add 1t1 o electrolytes containing non-.agueou s ventsenhibit markedly less attack upon the negatiye elec;

trode than d water andtheadu qusjelectmlxtes.

employed heretofore. It is the Object of the,iiiyentionte-n g id improved primary cell employing non-aqueous solvent in th electrolytein whic ce ll the negative electrode suffers only sligh attaclg by the electrolyte and does not undergo obiecti deterioration and exhaustion when 'the cellg snot in operation.

It is a further objectof- -theinvention m lgemetal;- suchas magnesium for the negative electrode, thus providing a cell having a higher voltage andreducing the number of cells required a battery of" predetermined voltage, and, in general; providing a battery capable of delivering a, high output of electrical energy for its. size. Another advantage obtained from the use of magnesium isthat it is one of the more abundant andread-ily-available-metals.

(other objects and advantages will become apparent as the following description progresses, which is .to be taken in conjunction with the accompanying drawing, in which the single figare is a sectional elevation ofa primary cell in accordance with the present invention.

The cell com-prises a container H! which is generallyrectangularin shape, but maybe of any desired shape, and-is open at the top. The container-is composed of a non-conductivemateri'al which is resistant to moisture and the electrolyte ofthe cell, such as rubber hydrochloride, phenol formaldehyde resin, or the like.

Adjacent to the interior surface of a wall of container H1 is the metal negative electrode 12 whichis in the form of a flat plate having a height somewhat lessthan that of the container 1:0 Adjacent-to the negative electrode is a layer of- =bibulous non-conductive material l3, such" as blotting-paper. I he bibulous layer I 3 absorbs the liquid electrolyte ofthe cell. Adjacentto thebibulous-layer- |'3-iS' a body of oxidizing material M- whichmay be a compacted liquid absorbent-massof finely divided particles of a mixture of conductive material, such as graphite, carbon blacle orother form of carbonjand an oxidizing agent which serves as a depolarizer for the cell. Said oxidizing agent will be described more fully; hereinafter. The proportions of oxidizing agent and conductive material are not critical, it being necessary only to provide sufficient eachto aitordthe desired conductivity and oxidizing activity. The oxidizing body l4 absorbs the electrolyte, whereby the electrolyte ispresent-in both the body I4 and the bibulous layer I3 Embedded in the oxidizing body [4 and in conductive contact-therewith is the positive electrode- !5 of thecell, which may be composed of an inert conductive substance and maybe in any desired form. In the specific cell shown, it is composed-.01". carbon' and the form of a cylin- .dr-icalzrod having itsupper end portion projecting abovethe oxidizing.- body- [4. The said pro- --l 0tingendhasa. metal: cap is fitting frictionally it possible to use amore highly eleotron wtive ill' b l Saidwapserving as one t rm al f the cell. The negative electrode l2 has a conductor I! connected thereto and serving as the second terminal of the cell. Conductor I! may be a strip of the same metal as that of which electrode [2 is composed, and may be connected to the electrode by welding. A sheet of nonconductive electrolyte-resistant material 18, which may be similar to the material of which container I is composed, is fitted into container l0 upon the tops of the cell elements. Th electrode l5 and terminal IT project upward y through the sheet l8. sealed by pouring into the upper portion of the container l0 and upon the sheet [8 a molten sealing composition, such as wax or pitch, which solidifies upon cooling to form the seal closure IS. The terminals I6 and I1 project above the sheet l8 and the seal l9 and are adapted for connection to an external circuit.

A liquid electrolyte is introduced into the container ID and is absorbed and retained by the bibulous layer 13 and the oxidizing body [4 and is in conductive contact with the negative electrode l2 and the oxidizing body 14. The electrolyte of the cell is a solution comprising a solvent component which is a non-aqueous liquid and a solute component which is a compound which renders the solution conductive and when in the solution is electrolytically reactive and spontaneously unreactive toward the negative electrode.

In accordance with the present invention, the solvent which may be employed is 2-propanone. This compound is a liquid at ordinary temperatures and by itself is inert toward the electrodes and the oxidizing agent, i. e., does not appreciably attack or corrode said elements.

Magnesium is employed for the negative electrode [2. Magnesium has the advantages that it is readily available, stable under most conditions, and produces a relatively high cell voltage.

For the positive electrode 15, a conductive material is chosen which is substantially inert toward the electrolyte, both in the presence and the absence of the electrolytic action of the cell. Carbon is suitable and where silver chloride is used as the oxidizing agent as described hereinafter, silver may be used. In the specific cell illustrated, the electrode I5 is a compressed body of carbon similar to that commonly used in dry cells of the LeClanche type.

For the reactive electrolyte compound, magnesium perchlorate is used. This compound is soluble in the organic solvent and forms therewith an electrolytically conductive solution. Also, when in solution in the solvent it is electrolytically reactive toward the material of the negative electrode, but is spontaneously unreactive toward said electrode, i. e., it is reactive toward the negative electrode when the cell electrodes are connected together through an external circuit and the cell is operative, and unreactive when the electrodes are not connected together and the cell is inoperative. Also, it does not cause the plating of metal on the negative electrode. The amount of reactive compound is not critical, it being only necessary to supply suflicient thereof to provide the desired reactivity and conductivity. During operation of the cell, the electrolyte enters into reaction with the negative electrode.

At ordinary temperature, magnesium perchlorate exists as the anhydrous compound, Mg(ClO4)z and also in the form of various hydrates including the dihydrate, Mg(ClO-1)2..2HzO, the trihydrate, Mg(C1O4)2.3H20, the tetrahy- The top of the cell is drate, Mg(C1O4)2.4H2.0 and the hexahydrate, Mg(C1O4)2.6I-I2O (J. A. C. S. vol. 54, pp. 3513-3523 (1932)). These hydrates, as well as the anhydrous compound, are suitable in the non-aqueous system of the present invention. When the solid hydrate goes into solution in the organic solvent, it continues to exhibit hydrating power, that is, the power to bind water, and the water of hydration remains bound thereto and the organic solvent remains free of water. In some instances a small amount of the water may become dissociated from the compound and exist in freedom in the solvent. Such water will then react with the negative electrode and cause a slight corrosion of the latter. Such water is quickly consumed, however, and does not do objectionable damage. and the solvent again as-- sumes its non-aqueous character. In the same way, the invention contemplates that a small amount of water may be present initially in the electrolyte. This water is quickly consumed in reacting with the negative electrode and the solvent then assumes its non-aqueous character. The solution of the reactive electrolyte compound in the solvent forms the electrolyte of the cell.

For the oxidizing agent which is included in the oxidizing body l4, manganese dioxide and silver chloride have been found to be suitable in accordance with the present invention. The oxidizing agent is one of the factors which determines the potential of the positive electrode.

The solution which has been described heretofore and which is held by the oxidizing body It and the absorbent layer [3 forms the electrolyte for the cell, providing electrolytic conductivity between the electrodes I2 and I5 and entering readily into electrolytic reaction with the negative electrode [2 and the oxidizing body I4, whereby the cell has strong current delivering powers.

A specific example of a satisfactory cell in ac-- cordance with the invention is one having the mechanical construction described heretofore and elements of the composition which will be described. The negative electrode is composed of magnesium and the positive electrode is composed of carbon. The solvent 2-propanone and the reactive electrolyte compound is magnesium perchlorate, which is present in an amount sufficient to produce a saturated solution at 20 C. Such an electrolyte provides satisfactory reactivity and conductivity. The oxidizing body [4 is a mixture, the solid components of which comprise approximately by weight of finely divided manganese dioxide and approximately 10% of thermal acetylene black. The separating member 13 is composed of blotting paper. Such a cell has an open circuit voltage of 1.62 volts, and is adapted to deliver current of substantial value.

This application is a continuation-in-part of our application Serial No. 713,944, filed December 4, 1946, now abandoned. Primary cells of a character generally similar to that described herein and employing variou organic solvents in the electrolyte are disclosed in our copending applications Serial Nos. 61,244, 61,245, 61,246, and 61,248, all filed November 20, 1948.

What is claimed is:

1. A primary cell comprising a magnesium negative electrode and a positive electrode, an electrolyte in contact with said electrodes comprising a substantially water-free 2-propanone solvent containing magnesium perchlorate dissolved therein, and an oxidizing body exposed to 5 said electrolyte and in conductive contact with said positive electrode.

2. A primary cell comprising positive and negative electrodes composed of carbon and magnesium respectively, an electrolyte in contact with said electrodes comprising a substantially waterfree 2-propan0ne solvent containing magnesium perchlorate dissolved therein, and an oxidizing agent composed of manganese dioxide exposed to said electrolyte and in conductive contact with said positive electrode.

3. A primary cell comprising a positive electrode and a magnesium negative electrode and an electrolyte in contact with said electrodes, said electrolyte comprising a substantially water-free 2-propanone solvent containing magnesium perchlorate dissolved therein.

JOSEPH J. COLEMAN. DEMETRIOS V. LOUZOS.

6 REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,425,163 Bardt Aug. 8, 1922 1,696,873 Wood Dec. 25, 1928 10 1,920,151 Ruben July 25, 1933 2,428,850 Lawson Oct. 14, 1947 FOREIGN PATENTS 15 Number Country Date 391,468 France Aug. '31, 1908 

3. A PRIMARY CELL COMPRISING A POSITIVE ELECTRODE AND A MAGNESIUM NEGATIVE ELECTRODE AND AN ELECTROLYTE IN CONTACT WITH SAID ELECTRODES, SAID ELECTROLYTE COMPRISING A SUBSTANTIALLY WATER-FREE 2-PROPANONE SOLVENT CONTAINING MAGNESIUM PERCHLORATE DISSOLVED THEREIN. 